Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/18—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide

Definitions

• the invention relates to a process for the hydroconversion of sulphur-containing heavy hydrocarbons with synthesis gas in the presence of steam in which synthesis gas and the hydrocarbons are reacted in a reactor at elevated temperature and pressure.
• Recycle gas from the hydroconversion reaction may be mixed with the synthesis gas.
• GB 257 256 discloses the conversion of coal or mineral oils into valuable liquid products by the action of hydrogen and carbon monoxide. The possible presence of sulphur in the material to be treated and the recycle of unreacted synthesis gas is mentioned.
• GB 400 844 and GB 407 127 disclose the hydrogenation of oil and coal/oil paste with hydrogen alone or with CO, H 2 S, steam.
• Hettinger et al are concerned with the hydroforming of relatively low boiling hydrocarbons to give gasoline, and sulphur is stated to have an adverse effect on this reaction.
• GB 2072697 discloses a heavy oil cracking process using synthesis gas (H 2 , CO).
• the gas recovered from the cold separator contains H 2 , CO, CO 2 and some impurities e.g. H 2 S and light hydrocarbon gases.
• H 2 S synthesis gas
• GB 2072697 describes passing the recycled gas through a scrubbing system. This scrubbing process will remove materials such as carbon dioxide and hydrogen sulphide. The hydrogen sulphide concentration in the recycled gas will therefore be low.
• hydrogen sulphide is stated to be an impurity and not a desirable constituent of the reaction mixture.
• a process for the hydroconversion of sulphur containing heavy hydrocarbons in which (1) a gas containing carbon monoxide and steam, and (2) the hydrocarbons are converted in a reactor at elevated temperature and pressure is characterised in that the gas fed to the reactor comprises at least 3% by volume of hydrogen sulphide, based on water free gas.
• the gas containing CO and steam used as a feed in the process of the present invention may be derived only from fresh synthesis gas with added steam or may also contain recycled unreacted gas. Where recycle gas is mixed with fresh synthesis gas the H 2 S content is calculated on the total volume of mixture.
• the process of the present invention is preferably carried out continuously.
• the hydrocarbons and the gas are heated in a pre-heating step before they are fed to the reactor.
• the gas fed to the reactor comprises at least 5% by volume of H 2 S.
• synthesis gas we mean a gas mixture principally of CO and H 2 obtained for example by gasification of fossil fuels such as lignite, crude oil, natural gas, coal, wood, heavy oil residues and the like or by steam cracking of normally gaseous or liquid light hydrocarbon fractions.
• a typical synthesis gas for use in the process of the invention contains CO and H 2 in various ratios to each other as well as distinguishable quantities of steam and small quantities of CO 2 , COS and lower hydrocarbons. The latter originate in particular from the recycle gas.
• Synthesis gas freed from hydrogen ie consisting mainly of CO can be used.
• H 2 is present.
• the process of the present invention may be applied to uncatalysed reactions e.g. hydrovis-breaking. However it is particularly useful to apply the process to reactions carried out in the presence of a catalyst. Thus the process may be applied to catalytic hydrocracking.
• Catalysts which can be used in the process of the invention are known for example from the above mentioned GB 1072697 as well as from DE OS 32 12 389.
• suitable catalysts are carbonaceous solids e.g. coal, coke or charcoal, which may be coated with up to 20% wt of a metal catalyst such as iron group metal
• iron, nickel, cobalt iron, nickel, cobalt
• molybdenum zinc, tin, tungsten, chromium.
• the catalysts can be used in finely divided suspended form ("slurry phase"), as an ebulliated bed or as a solid bed.
• the catalysts quantities employed in the "slurry phase” method are for example 0.2-5% by weight, calculated on the hydrocarbon feed.
• the steam required for the reaction can be added together with the fresh feed gas, or fresh gas and recycle gas, or can be added separately.
• the quantity of steam used will depend on the quantity of hydrogen fed to the reactor as it is believed that the water produces hydrogen by the shift reaction. An excessively high proportion of steam will reduce the partial pressure of the CO. The optimum quantity can be found by simple tests.
• the quantity of steam may be defined by the amount of liquid water used to produce the steam. The optimum amount of liquid water will in general be within the range 10 to 1000 ml liquid water per kg of liquid hydrocarbon fed, for example 20-200 ml of water per kg of liquid hydrocarbon fed.
• the reaction temperature is typically 300-500°C and the reaction pressure 1.5-30 MPa.
• heavy hydrocarbons which can be used are for example atmospheric or vacuum residues from crude oil distillations as well as heavy hydrocarbons from tar sands and oil shales.
• the hydrocarbon is introduced to the reactor with a LHSV rate of 0.2-10 1/1/h in continuous processes.
• the ratio of gaseous feed to hydrocarbon is preferably in the range 500-50001/kg (litres gas at normal temperature and pressure (0°C, 0.1 MPa pressure) per kg of hydrocarbon).
• this gaseous feed can consist of fresh synthesis gas only (and steam) or synthesis gas and recycle gas (and steam) .
• any recycled unreacted gas will be treated so as to remove impurities, and this will result in removal of most of any hydrogen sulphide present.
• hydrogen sulphide must be added.
• the hydrogen sulphide may be hydrogen sulphide produced in the reactor from sulphur-containing compounds and which is recovered from the gas treatment step. Such recovered hydrogen sulphide may be added back to the recycle gas immediately after the gas treatment step, or may be added to the fresh gas feed, or to the mixture of fresh and recycle gas. It may be desirable to use hydrogen sulphide which is not produced In the process, particularly on starting the plant or when using a feed with a relatively low sulphur content. Thus hydrogen sulphide can also be introduced from other sources e.g. from a Claus process.
• Increasing hydrogen sulphide content in the reaction system can lower the partial pressure of hydrogen and carbon monoxide to such an extent that the degree of conversion of the heavy hydrocarbon declines; the practical upper limit for the hydrogen sulphide content In the system can however be determined easily by the person of ordinary skill for each individual case.
• the H 2 S content of the feed gas preferably does not exceed 20% volume.
• the apparatus comprises a hydrocracking reactor 1, which can consist of one or more similar reactors arranged In series, one or more hot separators 2 giving a first coarse separation of the hydrocracking product, one or more reactors 3 in which a post hydrogenation of unsaturated hydrocarbons takes place e.g. in a solid bed with Co/Mo or Ni/Mo-catalysts takes place, as well as a section 4 for gas and product separation in the form of for example a plurality of product separators working with or without pressure, and further apparatus for gas separation such as wash towers, membrane and/or low temperature separation stages.
• a hydrocracking reactor 1 can consist of one or more similar reactors arranged In series, one or more hot separators 2 giving a first coarse separation of the hydrocracking product, one or more reactors 3 in which a post hydrogenation of unsaturated hydrocarbons takes place e.g. in a solid bed with Co/Mo or Ni/Mo-catalysts takes place, as well as a section
• the reactor 1 is provided with a mixture of heavy hydrocarbons and catalyst through line 5.
• line 5 there are one or more pumps and preheater stages 7.
• Synthesis gas is led through line 8
• H 2 S is led through line 9.
• Unconverted or insufficiently converted hydrocarbon material separated in hot separator 2 is removed by line 13 or is partly recycled to the conversion reaction through line 14.
• H 2 S and synthesis gas are taken off separately through lines 15 and optionally returned to the process.
• Lines 16 serve for removal of CO 2 , C 1 -C 3 hydrocarbons as well as higher hydrocarbons.
• the heavy liquid hydrocarbon feedstock used in these experiments was an atmospheric residue (derived from a Boscan crude) with the following characteristics:
• the autoclave is pressurised to 80 bar (8 MPa)with hydrogenating gas, heated quickly to 440°C, maintained at this temperature for one hour, and then cooled down.
• Comparative Test D shows that the use of mixtures of CO and H 2 S give very high coke yields. Such results would not encourage any one to believe that hydrogen sulphide was in any way satisfactory as a hydrogenating gas.
• C 1 -530°C is slightly lower when H 2 S is used while the amount of the less desirable high boiling material (boiling at temperatures above 530°C) is higher when H 2 S is added.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Hydrogen, Water And Hydrids (AREA)

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Cited By (2)

Citations (5)

• 1985
  • 1985-04-11 WO PCT/GB1985/000159 patent/WO1985004670A2/en unknown
  • 1985-04-11 JP JP50158585A patent/JPS61501855A/ja active Pending
  • 1985-04-11 EP EP19850302550 patent/EP0159867B1/en not_active Expired
  • 1985-04-12 ES ES542204A patent/ES8606465A1/es not_active Expired

Patent Citations (5)

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